CN101657255B - Catalyst for the preparation of methyl mercaptan - Google Patents

Catalyst for the preparation of methyl mercaptan Download PDF

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CN101657255B
CN101657255B CN200880012113.6A CN200880012113A CN101657255B CN 101657255 B CN101657255 B CN 101657255B CN 200880012113 A CN200880012113 A CN 200880012113A CN 101657255 B CN101657255 B CN 101657255B
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catalyst
acid
carrier
compound
moo
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CN101657255A (en
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J-O·巴尔特
H·雷德林绍弗尔
C·韦克贝克
K·胡特马赫尔
H-W·赞托夫
R·迈尔
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Evonik Operations GmbH
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Evonik Degussa GmbH
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/36—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding

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Abstract

The present invention refers to a catalyst for the manufacture of methyl mercaptan from carbon oxides comprising Mo and K compounds and oxides or sulfides of metals chosen from the manganese group. The improvement of the present process consists of the fact that carbon dioxide can be converted with higher conversions and selectivities to methyl mercaptan as compared to state-of-the-art technologies, with only minor amounts of carbon monoxide being formed as side product. Simultaneously, carbon monoxide can be easily converted into carbon dioxide and hydrogen by reaction with water using established water-gas-shift-technologies thus increasing the overall selectivity to methyl mercaptan.

Description

For the preparation of the catalyst of methyl mercaptan
Technical field
The present invention relates to the catalyst for producing methyl mercaptan from the oxide of carbon, described catalyst comprises the compound of Mo, K and is selected from the transition metal of metal of periodic table of elements manganese race, the especially compound of Mn and Re.
The invention still further relates to the method for the preparation of described solid catalyst system.
Background technology
Methyl mercaptan is for the preparation of organic compound, the well-known intermediate of the amino acid of such as sulfur-bearing, pesticide and dyestuff.Industrially, methyl mercaptan is also known as methyl mercaptan, is mainly produced to synthesize methionine, a kind of widely used poultry feed addictive.
Prepared by the industrial heterogeneous catalysis gas-phase reaction by methyl alcohol and hydrogen sulfide of methyl mercaptan.Such as, EP-B-0832878 and DE-C-19654515 discloses based on hydrogen sulfide (H 2s) with methylol (CH 3oH) methyl mercaptan preparation method.EP-A-167,354 synthesis paths disclosing the reaction based on hydrogen sulfide and carbon monoxide (CO), wherein use titanium dioxide (TiO 2) as carrier, and use nickel oxide (NiO) or molybdenum oxide (MoO 3) as active component.
Chinese patent application CN 1207957 and CN 1207958 discloses for from containing high H 2a series of catalyst of the synthesis gas synthesizing methane mercaptan of S, wherein, active component (Mo-S-K-substrate matter) is from precursor K 2moS 4, or NH 4) 2moS 4and sylvite.In these in state's patent application, dimethyl formamide instead of water are selected as solvent with lytic activity component.Described method is restive and expensive.
WO 2005/040082A2 relates to the method utilizing the continuation method of Mo-O-K catalyst based production methyl mercaptan and the preformed catalyst system for the preparation of solid.It also describes the overall selectivity increase at least 1% making methyl mercaptan by reducing total gas hourly space velocity.
EP-A-104507 describes the continuation method of oxide, sulphur or hydrogen sulfide and the hydrogen reacting carbon under high pressure-temperature.Reaction is carried out on the preformed monophase solid catalyst system comprising the support containing Woelm Alumina, and described support deposits the mixture of manganese sulfide and at least one chosen from Fe, nickel, zinc, chromium, cobalt, molybdenum or alkali-metal sulfide.Described method is under the catalyst system of the specific sulfur-bearing containing manganese or sulfide exists, prepare the continuous gas-phase reaction of methyl mercaptan, and it has conversion ratio and the yield of raising.Wherein mention that, by using described catalyst system, the formation of methane remains on minimum, and this achieves the economic process of improvement.Such as the formation of methane of inertia accessory substance should be avoided because these inert substances are difficult to be separated from circulating air.It piles up and needs emptying termly in circulating current.
Carbonyl sulfide, dimethyl sulfide, carbon disulfide and methyl disulfide is comprised by other accessory substance of the oxide of carbon, sulphur or hydrogen sulfide and hydrogen synthesis of methyl mercaptan.Especially the formation of carbonyl sulfide should remain on minimum because carbonyl sulfide is intermediate in formation methyl mercaptan.The low selective of carbonyl sulfide makes the selective higher of methyl mercaptan, therefore improves the total recovery of methyl mercaptan and total economy of method.
US 4,665,242 describes by the method for heat packs under existing based on the catalyst of tungsten sulfide or rheium oxide in active oxidation aluminum matrix containing the gas generation methyl mercaptan of carbon monoxide and/or carbon dioxide, hydrogen sulfide and hydrogen.In the method, unreacted gas is circulated to feed gas stream, wherein, with catalyst reaction during the water that formed shift out from unreacted gas.By gas is carried out drying by molecular sieve.Report and use Re 2o 7/ Al 2o 3catalyst, at CO 2-conversion ratio is the maximum selectivity under 28.0% is 64.6%.
Although carried out countless trial to improve from the selective and yield of the Preparation methyl mercaptan of carbon, still need further raising, because of ideally methyl mercaptan selective higher under the conversion ratio of the oxide of relatively high carbon.Especially, carbon dioxide is attractive as the Cl source for methyl mercaptan, because main byproducts of carbon monoxide easily can be converted into carbon dioxide, thus improves the overall selectivity of methyl mercaptan.
Goal of the invention
An object of the present invention is to provide for the oxide from carbon, preferably carbon dioxide prepares the catalyst of methyl mercaptan, and described catalyst has the selective and yield of high methyl mercaptan under relatively high carbon dioxide conversion.
Summary of the invention
The present invention relates at high temperature and pressure by comprising the oxide metal oxygen-containing compound that is selected from manganese race metal or sulfur-containing compound and Mo-O-K-base activated centre, co-catalyst and the catalyst of carrier contacting carbon, the immixture (intimatemixture) of preferably carbon dioxide, sulphur or hydrogen sulfide and hydrogen and prepare the catalyst of methyl mercaptan.
Unexpectedly, have been found that based on selected reaction condition, be greater than 50% time at one way titanium dioxide charcoal percent conversion, the overall selectivity of methyl mercaptan is increased to and is greater than 80% by using catalyst according to the invention.Also finding, by using containing the transition metal being selected from manganese race, being preferably deposited on the TiO of selection 2catalyst of the present invention on carrier is used for preparing methyl mercaptan from carbon dioxide, and what can keep byproducts of carbon monoxide is always formed as absolute minimum.Notice by easily carbon dioxide can be converted into water carbon monoxide of reaction, because this increasing the global selectivity of methyl mercaptan.
In addition, utilize above-mentioned catalyst, under the reaction condition of method described herein, by byproduct methane (CH 4), dimethyl sulfide (DMS) and carbon disulfide (CS 2) formation remain on minimum.This effect realizes being significant advantage for the technology of the method, because by inert gas, the formation as methane that must be emptying termly remains on definitely minimum.And, optimize the abstraction and purification of product methyl mercaptan (MC), because only define the accessory substance of trace in the method, as carbon disulfide, dimethyl sulfide and methane.
Another object of the present invention is the method for the catalyst system for the preparation of solid of the present invention.
Detailed Description Of The Invention
The present invention relates to a kind of catalyst and the method preparing methyl mercaptan, it comprises the oxide (CO of carbon 1-2), as carbon monoxide (CO) or carbon dioxide (CO 2), sulphur or hydrogen sulfide, contact the preformed catalyst of described solid at high temperature under high pressure with the immixture of hydrogen, described catalyst comprises active component, co-catalyst and carrier, and unreacted gas fraction is circulated to the feed stream in the method.
Progress of the present invention is the following fact: compared with prior art, and carbon dioxide can with higher conversion ratio and higher methyl mercaptan be selective is converted, and only forms the carbon monoxide of trace as accessory substance.Meanwhile, reacting by using existing Water gas shift/WGS technology and water to be easily carbon dioxide and hydrogen by monoxide conversion, thus adds the global selectivity of methyl mercaptan.
Catalyst according to the invention comprises:
A) containing Mo and the oxygenatedchemicals containing K, wherein, Mo and K can be the composition of same compound,
B) element of the manganese family element of the periodic table of elements is selected from, especially the active oxygenatedchemicals A of Mn or Re xo y;
C) the optional co-catalyst existed, it is selected from the oxygenatedchemicals M of transition metal and rare earth metal xo y;
D) replace or except M xo youtside, the optional SnO existed 2;
E) containing the carrier of oxygen or active carbon, exception is that catalyst comprises rheium oxide or sulfuration rhenium if aluminium oxide is used as carrier.
Containing Mo and the part being preferably positioned at the active Mo-O-K phase on the surface of supporting body material containing the compound of K.
The present invention can also be practiced in catalyst described in hydrogen sulfide treatment.Then, the oxygenatedchemicals of described catalyst is converted into sulfide or sulfohydrate at least in part.
This means that the catalytic active component of catalyst is oxygenatedchemicals or described sulfur-containing compound or the mixture of the two.
Catalyst according to the invention comprises the active component be made up of the oxygenatedchemicals of the metal being selected from manganese family element or sulfur-containing compound, Mo and K compound, its oxygenatedchemicals or sulfur-containing compound, or the mixture of the two, co-catalyst and carrier.The oxide of the oxide of described manganese or sulfide or rhenium or the precursor of sulfide are such as manganese acetate, manganese carbonate, perrhenic acid (HReO 4) and rhenium heptoxide (Re 2o 7).The example of use amount is for purposes of the present invention relative to total catalyst weight, the MnO of 1-50 % by weight 2or the Re of 1-50 % by weight 2o 7.
The weight ratio of described oxide is:
A xo y/ K 2moO 4/ carrier=0.001/0.01/1-0.5/0.8/1
A xo y/ MoO 3/ K 2o/ carrier=0.001/0.01/0.005/1-0.5/0.8/0.5/1, preferably,
A xo y/ K 2moO 4/ carrier=0.001/0.05/1-0.3/0.5/1
A xo y/ MoO 3/ K 2o/ carrier=0.001/0.05/0.03/1-0.3/0.5/0.3/1
Wherein A refers to Mn or Re, and x and y is the integer of 1-7.
The precursor in Mo-O-K-base activated centre is such as potassium molybdate (K 2moO 4) or ammonium heptamolybdate [(NH 4) 6mo 7o 24] x 4H 2o and sylvite, or MoO 3and potassium compound.Potassium acetate (KAc) is selected from, potassium oxalate (K for the potassium compound in the present invention or salt 2c 2o 4), potassium hydroxide (KOH), potash (K 2cO 3), potassium nitrate (KNO 3) and saleratus (KHCO 3).Sylvite is soluble in water and be placed on supporting body material with amount of calculation, and this was carried out usually before or after being deposited by the remaining ingredient of catalyst by dipping well known by persons skilled in the art or coating technique.The example of consumption that has for the sylvite of the object of the invention is the K of the 1-50 % by weight of total catalyst weight 2o, the K of preferred 10-30 % by weight 2o.
By various method well known by persons skilled in the art, such as, be applied to the multistep dipping of carrier surface or use active component coating carrier, with different catalyst components dipping or coating catalytic agent carrier.Active catalyst block can be pressed, extrude or granulation has the catalyst of various 3D shape and size with preparation.
Other co-catalyst useful in catalyst of the present invention is by formula M xo yrepresent, wherein, M is selected from transition metal and rare earth metal.Specially suitable co-catalyst is chosen from Fe (Fe), cobalt (Co), nickel (Ni), the oxide of the metal of lanthanum (La) and cerium (Ce), x and y is the integer of 1-5.Except M xo youtside or replace M xo y, catalyst optionally comprises SnO 2.Carrier available in the present invention is preferably selected from silica (SiO 2), titanium dioxide (TiO 2), zeolite or active carbon.Only when catalyst comprises rheium oxide or sulfuration rhenium, only use aluminium oxide.
When containing Mo component with K 2moO 4amount when representing, K 2moO 4/ M xo ythe weight ratio of/carrier equals (0.01-0.80)/(0.01-0.1)/1, preferably (0.10-0.60)/(0.01-0.06)/1.But, when described component is by MoO 3and K 2when the amount of O represents, MoO 3/ K 2o/M xo ythe weight ratio of/carrier equals (0.10-0.50)/(0.10-0.30)/(0.01-0.10)/1, preferably (0.10-0.30)/(0.10-0.25)/(0.01-0.06)/1.
Advantageously, available in the present invention support is selected from titanium dioxide (TiO 2).The catalytic activity of catalyst can be greater than 25m by using surface area 2the supporting body material of/g improves.Advantageously, there is surface area at least 40m 2/ g and anatase content are greater than the titanium dioxide support of 60% as catalyst carrier.For actual techniques object, before or after impregnation technology, high surface titania support is extruded or granulation.Preferably, by Degussa Aerolyst tMcarrier or similar high surface titania source are used as support.
The shape of support is not crucial for the performance of catalyst of the present invention, and it can be three-dimensional spherical, cylindrical, annular, starlike, granular or other 3D shape or can be pressed, to extrude or granulation is the powder type of 3D shape.Advantageously, catalyst granules has uniform domain size distribution (NMD: 5% is characterised in that particle diameter is 0.2mm-20.0mm).
The invention still further relates to the method for the preformed catalyst system preparing solid, it comprises the steps:
I) preparation comprises compound containing manganese or rhenium-containing and K 2moO 4, or (NH 4) 6mo 7o 244H 2o and potassium compound or MoO 3with the aqueous solution or the aqueous solution of the salt of potassium compound and the optional transition metal that exists or rare earth metal; With
II) with the carrier that described solution impregnation is suitable, the intermediate of dry preparation subsequently, calcines described intermediate to obtain catalyst; With
III) optionally, by with sn-containing compound as tributyltin acetate floods, with the SnO of 1-50 % by weight 2the catalyst that modification obtains, wherein, selects the content of described tin compound to make it reach the SnO of 1-50 % by weight 2content.
Or according to the present invention, can be prepared the method for the catalyst system of solid with multi-step dipping, it comprises the steps:
A) preparation comprises the aqueous solution containing the compound of manganese or rhenium-containing and the salt of the optional transition metal that exists or rare earth metal or aqueous solution;
B) with the carrier that described solution impregnation is suitable, dry obtained intermediate, optionally calcines described intermediate subsequently;
C) K is prepared 2moO 4, or (NH 4) 6mo 7o 244H 2o and potassium compound or MoO 3with potassium compound containing water soaking solution (steeping solution); With
D) intermediate prepared under being immersed in (B) with the aqueous solution of preparation under (C), the then catalyst of drying and calcining gained.
E) optionally, with the SnO of 1-50 % by weight 2the catalyst that modification obtains, wherein, described catalyst sn-containing compound such as tributyltin acetate floods, dry, optionally calcines.
Sequence of steps can also be changed.
An example of preparation catalyst according to the invention can be as follows:
1. by the manganese of specified rate or the salt of rhenium, as nitrate, acetate or similar salt are dissolved in the distilled water of specified rate to prepare aqueous solution, with the carrier 3-5 hour of the selection of described solution impregnation specified rate, subsequently at 50-130 DEG C of dry 1-3 hour to prepare intermediate.Subsequently, at 300-600 DEG C, calcine the solid material 5-6h of gained.
2. by the K of specified rate 2moO 4, or (NH 4) 6mo 7o 24with potassium compound or MoO 3be dissolved in the distilled water of specified rate with potassium compound, with the intermediate 7-9 hour of described solution impregnation preparation in step (1), dry 2-4 hour at 50-130 DEG C, calcines 2-4 hour at 400-500 DEG C subsequently.
3. obtained catalyst, by catalyst being suspended in sn-containing compound as in the solution of tributyltin acetate, removes desolventizing subsequently to prepare the SnO of content for 1-50 % by weight 2catalyst and optionally modification.
Preferably described catalyst is at high temperature exposed to hydrogen sulfide containing atmosphere, makes the oxygenatedchemicals of catalyst be converted into sulfur-containing compound at least in part, as sulfide or sulfohydrate.
Optionally, in order to strengthen the formation of catalytic active substance, with alkylamide as dimethyl formamide and dimethylacetylamide, or organic acid process steeping liq and/or the dipping solution of at least one carbon atom and at least one acid functional group can be comprised.Useful especially in method for preparing catalyst is organic acid, as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, propiolic acid, vinyl acetic acid, methacrylic acid, crotonic acid, 4-penetenoic acid (4-pentanoic acid), sorbic acid, oxalic acid, malonic acid, butanedioic acid, maleic acid, 3-hydroxybutyrate, glutaric acid, adipic acid, citric acid, tartaric acid or ethylenediamino tetraacetic acid, citric acid is especially preferred.
About present disclosure, particular term has following implication as used herein:
Term " active catalyst block " refers to the composition of the catalyst support (carrier) with the various mixed oxide dipping or coating representing catalytic active substance.
Term " catalytic active component " refers to the oxide of metal or sulfide or sulfohydrate, and it is with the compound dipping of described metal or be present on the surface of carrier after covering.
The term " support " used and " carrier " have identical implication.This term refers to the porous material with various three dimensional form and size, and provides high specific area.
Term " single-phase " solid catalyst refers to the catalytic activity block of tight blending ingredients, and it is solid material and optionally floods or be deposited on support or carrier material.
Term " co-catalyst " to refer to before or after sulfuration transition metal oxide or hydroxide or transient metal sulfide or sulfohydrate or transition metal salt precursor.
Term " sulfide " refers to the material comprising simple sulfide and sulfohydrate and complicated sulfide as used herein.
Term " sulfuration " or " sulfuration " refer to that at high temperature processing active catalyst block a period of time with the elementary sulfur of hydrogen sulfide or gaseous state or liquid state and hydrogen is converted into sulfide at least in part to make the active component of catalyst as used herein.Catalytic active substance is converted into sulfide state from oxide, hydroxide or other salt any and will changes the weight of compound to a certain extent.But, before sulfuration, can allow to use the sulphide precursor within the scope of identical weight described herein to provide the catalyst system defined in the present invention for sulfide.
Term " (during gas) air speed " refers to the cumulative volume (usually to be upgraded to unit) measured at standard temperature and pressure by the oxide of the carbon of catalyst system unit volume (being generally 1 liter), hydrogen and hydrogen sulfide in hour as used herein.
Term " yield " refers to 100 moles of often initial actual CO or CO being converted into methyl mercaptan or other specific accessory substance any 2molal quantity.
Term described herein " conversion ratio " refers to and is converted into methyl mercaptan or other mole percent of carbon dioxide of product any, and the fractional percentage producing methyl mercaptan is defined as selective individually.
Therefore, yield=conversion ratio × selective
For method of the present invention, carbon dioxide, hydrogen sulfide or elementary sulfur and hydrogen are preferred initial substances.That carbon monoxide can be used for replacement part or whole carbon dioxide, but find that carbon dioxide provides higher methyl mercaptan selective than carbon monoxide.
Carbon monoxide and hydrogen are also known as synthesis gas with the mixture of various stoichiometric proportion and easily prepare by various method, as partial oxidation, the steam reformation of natural gas, the high pressure residue from crude distillation or coal gasification of hydro carbons.The extensively known method of the steam reformation of natural gas (methane) can be expressed from the next:
CH 4+ H 2o → CO+3H 2(formula 1)
By adding water, monoxide conversion is carbon dioxide and hydrogen, is represented by formula 2.Notice total CO 2/ H 2than being that 1/4 (formula 3) makes it be for the desirable feed gas (formula 7) from carbon dioxide, hydrogen and sulphur synthesis of methyl mercaptan.
CO+H 2o → CO 2+ H 2(formula 2)
CH 4+ 2H 2o → CO 2+ 4H 2(formula 3)
Hydrogen sulfide can be conducted to this process or can be formed on the spot in this process, by before it is contacted with the reaction-ure feeding in reactor, period or react the elementary sulfur of melting or steam-like afterwards.Elementary sulfur directly can be supplied to reactor with the oxide of carbon together with hydrogen, because under temperature and pressure condition of the present invention, sulphur will be in molten condition and form H immediately when contacting with hydrogen 2s.Chemical reaction is as follows:
CO+H 2s+2H 2→ CH 3sH+H 2o (formula 4)
CO 2+ H 2s+3H 2→ CH 3sH+2H 2o (formula 5)
CO+S+3H 2→ CH 3sH+H 2o (formula 6)
CO 2+ S+4H 2→ CH 3sH+2H 2o (formula 7)
It is believed that on catalyst described herein, by the hydrogenation of the carbonyl sulfide (COS) of centre, reaction is carried out, and described carbonyl sulfide is formed when the reaction of carbon monoxide or carbon dioxide and hydrogen sulfide:
CO+H 2s → COS+H 2(formula 8)
CO 2+ H 2s → COS+H 2o (formula 9)
COS+3H 2→ CH 3sH+H 2o (formula 10)
For method described herein, have been found that the catalyst of the application of the invention, the yield of intermediate carbonyl sulfide can minimize, and by utilizing the catalyst comprising the transition metal of manganese race, makes the yield of methyl mercaptan increase thus.Preferably, the selective height being presented at methyl mercaptan under the high conversion of carbon dioxide containing rhenium compound is used.
And, by using catalyst described herein, having been found that and can not to occur as within the scope of the oxide of carbon and the methyl alcohol of the product of hydrogen and the formation of dimethyl ether temperature and pressure described herein.Result is, use carbon dioxide as carbon source, only carbon monoxide, methane, carbonyl sulfide, carbon disulfide and dimethyl sulfide are only potential byproducts of reaction, and what be attended by trace reacts by fischer-tropsch type higher (gathering) sulfide and hydro carbons of being formed.
Total gas hourly space velocity is reported as at this by the feeding rate of the reactant of the beds of reactor.Reaction of the present invention can be 1-10000h in air speed -1, preferred 100-5000h -1more preferably 300-3000h -1range of operation.Optimum use air speed will at 450-3000h -1between change, depend on other condition of method, as the mol ratio of temperature, pressure and reactant.Have been found that air speed is lower, methyl mercaptan selective higher, the formation of undesirable accessory substance as carbonyl sulfide and methane is fewer.
The mol ratio of the reactant in feed mixture, namely the oxide of carbon, hydrogen sulfide or elementary sulfur and hydrogen should be selected to make hydrogen sulfide excessive.Preferably, CO 1-2/ H 2s/H 2mol ratio be 1/1/0 to 1/8/8, preferably 1/2/1 to 1/4/4.H is replaced when using elementary sulfur in feed 2during S, reactant CO 1-2/ S/H 2s/H 2mol ratio will be preferably 1/1/0/1 to 1/8/8/8, more preferably ,/2/2/1 to 1/4/4/4.Be shown below, the existence of hydrogen is not prerequisite for formation methyl mercaptan.Utilize method of the present invention and catalyst, when hydrogen does not exist, by using H 2s easily can form methyl mercaptan as sulphur source.
3CO+2H 2s → CH 3sH+COS+CO 2(formula 11)
For chemical reaction, it is favourable for utilizing a series of fixed catalyst bed or the reactor that comprises one or more (n=1-10) conversion zones to carry out method of the present invention, wherein one or more reacting gas can between conversion zone feed.Catalyst can be arranged in the fixed bed or multitubular reactor with intermediate gas inlet, to carry out better temperature control.
According to the preferred embodiment of method of the present invention, by the oxide of carbon reactant, sulphur, hydrogen sulfide and hydrogen infeed reactor before with desirable mixed in molar ratio.Reactant can in different regions/beds be set in sequence in reactor introduces the overall yield increasing methyl mercaptan independently.Preferably, between beds, introduce hydrogen and/or hydrogen sulfide, increase the overall yield of methyl mercaptan thus.
Before entering the reactor, reactant is advantageously preheated at least 120 DEG C.Preferred preheat temperature is 120-350 DEG C.Use elementary sulfur as sulphur source, reacting gas can be fed by liquid sulfur at temperature preferred 140-450 DEG C, or can mix with gaseous sulfur before entering the reactor.
Temperature in reactor is controlled by the temperature of beds usually, scope be at least 200 DEG C to not higher than 500 DEG C, preferably 250-400 DEG C, more preferably 220-350 DEG C.When sulphur is used as the reactant in the method, the temperature and pressure in reactor should at least enough maintain sulphur and be in liquid state.Although reaction is heat release, need outside additionally heat supply.
Have been found that in the method for the invention, the formation of byproducts of carbon monoxide can by increasing reaction temperature and being converted into carbon dioxide subsequently and minimizing gradually.This effect is the formation that the favourable increase being reaction temperature can be conducive to accessory substance.Pressure in reactor usually above 5bar, preferably >=10bar.In order to increase the yield of methyl mercaptan, pressure is preferably 15-50bar, more preferably 20-40bar.
Before starting the reaction, catalyst in the air-flow of hydrogen sulfide air-flow or hydrogen sulfide, hydrogen and carbon dioxide at 20-500 DEG C, preferred 200-400 DEG C, preconditioned under pressure 1-50bar.Subsequently, catalyst is exposed in the air-flow of hydrogen sulfide or hydrogen and elementary sulfur and carbon dioxide at reaction conditions.The total time of preconditioned process is 1-48 hour, preferred 2-24 hour.
The present invention is described by embodiment in more detail following.
Embodiment
embodiment 1
Kaolinite Preparation of Catalyst A-E
catalyst A
Perrhenic acid (the HReO of preparation 2.0635g 4) be dissolved in aqueous solution in 20ml distilled water.With this HReO of 18ml 4-solution floods the TiO of 50g with continuous stirring 2-support.The support of dipping is stirred 5 minutes, at room temperature aging 30 minutes subsequently.Then, drying material 4.5 hours at 100 DEG C in an oven.The potassium molybdate of preparation 23.73g is dissolved in the aqueous solution in the distilled water of 25ml.With the K of 18ml 2moO 4the support of-solution coating dipping.The carrying out that second dipping is similar with the first impregnation steps.After at room temperature aging 30 minutes, catalyst at 100 DEG C dry 2 hours in an oven, subsequently 500 DEG C of calcinings 1 hour.
catalyst B
Preparation 0.5882g tributyltin acetate is dissolved in the ethanolic solution in the ethanol of 31.9g.With this solution 50 DEG C of catalyst A of flooding 19.8g under continuous rotation 1.5 hours.Subsequently, shift out ethanol under vacuo, calcine 2 hours at 150 DEG C subsequently.
catalyst C
The manganese acetate x 4H of preparation 4.291g 2o is dissolved in the aqueous solution in the distilled water of 20ml.Under continuous rotation with the TiO of this Mn-acetate solution of 18ml coating 50g 2-support.Stir the support 5 minutes of this dipping, at room temperature leave standstill aging 30 minutes, then in an oven at 100 DEG C dry 4.5 hours.The potassium molybdate of preparation 23.73g is dissolved in the aqueous solution in the distilled water of 25ml.With the K of 18ml 2moO 4the support of-solution coating dipping.After aged at room temperature 30, dry catalyst 2 hours at 100 DEG C in an oven, then calcining 1 hour at 500 DEG C.
catalyst D
Under agitation by the K of 31.7g 2moO 4be dissolved in (pH ~ 9.5-10) in the distilled water of 65ml.The citric acid of 26.7g is added to this solution in batches.Subsequently, add the manganese acetate of 10.7g and dissolve.By the TiO of steeping liq (pH ~ 5.5) with 75g 2-support contacts, and described support impregnation 24 hours, then filters, dry under room temperature.Finally, dry catalyst 2 hours at 80 DEG C, calcines 1 hour at 500 DEG C in an oven.
catalyst E
Prepare the solution that manganese acetate is dissolved in 5% in distilled water.By the γ-Al of 50g be suspended in distilled water 2o 3supporting body material is often criticized 10ml and is added to this dipping solution under stirring continuously.Subsequently, stir this suspension 5 minutes, aging 30 minutes of left at room temperature.Catalyst at room temperature dry 1 day, in an oven at 100 DEG C dry 2 hours subsequently.Prepare the aqueous solution of cesium hydroxide.With the support of this CsOH-solution coating dipping.Aged at room temperature is after 30 minutes, and catalyst at 80 DEG C dry 2 hours in an oven, be cooled to room temperature, at 500 DEG C, calcining has 19m%MnO to prepare load in 1 hour subsequently 2with the catalyst of 10m%CsOH.
embodiment 2
Catalyst A-E under following reaction condition described in testing example 1: total gas hourly space velocity is 750-3000h -1, the mol ratio CO of reactant 2/ H 2/ H 2s is 1/4/4 respectively, and reaction bed temperature is 250-350 DEG C (maximum), and absolute pressure is 30bar.The one way catalyst activity of assessing reactor.Conversion ratio and optionally mensuration are as mentioned above.
Table 1
Catalyst Carrier Conversion ratio (CO 2)/％ Selective (MC)/ Selective (CO)/% Selective (CH 4Or COS)/%
Catalyst A Re 2O 7/K 2MoO 4/TiO 2 TiO 2 55.8 82.2 11.8 4.5 (CH 4)
Catalyst B SnO 2/ Re 2O 7/K 2MoO 4/TiO 2 TiO 2 53.5 82.6 9.9 4.8 (CH 4)
Catalyst C Mn xO Y/K 2MoO 4/TiO 2 TiO 2 50.1 81.5 12.6 3.5 (CH 4)
Catalyst D Mn xO Y/K 2MoO 4/TiO 2 TiO 2 48.5 80.4 13.9 3.4 (CH 4)
Catalyst E MnO 2/CsOH/Al 2O 3 Al 2O 3 33 3.8 81.4 14.5 (COS)
CO 2=carbon dioxide
MC=methyl mercaptan
embodiment 3
Table 2 shows the Re with prior art 2o 7-Al 2o 3catalyst is compared and is immersed in DegussaAerolyst TiO 2on carrier by SnO 2-Re 2o 7-K 2moO 4-TiO 2the catalytic activity of the catalyst of composition, its load has the SnO of 1 % by weight 2.Test material under following reaction condition: total gas hourly space velocity is 400-3000h -1, reactant molar ratio is respectively CO 2/ H 2/ H 2s is 1/4/4, and reaction bed temperature is 250-400 DEG C, and absolute pressure is 30bar.The one way catalyst activity of assessing reactor.Conversion ratio and optionally mensuration are as mentioned above.Notice and be immersed in Al 2o 3re on-supporting body material 2o 7catalyst is compared, and the formation of carbon monoxide and methane reduces, and the selective and yield of methyl mercaptan significantly increases.
Table 2
Catalyst Conversion ratio (CO 2)/％ Yield (MC)/% Selective (MC)/% Selective (CO)/% Selective (CH 4)/％
1 % by weight SnO 2-Re 2O 7- K 2MoO 4-TiO 2 53.5 44.2 82.6 9.9 4.8
3.25％Re 2O 7/Al 2O 3 28.0 18.1 64.6 25.2 7.9
embodiment 4
Detecting catalyst A under following reaction condition: total gas hourly space velocity is 750h -1-3000h -1, reactant molar ratio is CO 2/ H 2/ H 2s is 1/4/4, and reaction bed temperature changes between 220 DEG C (minimum) to 340 DEG C (the highest), and absolute pressure is 30bar.The one way catalyst activity of assessing reactor.Fig. 1 and 2 display is as CO 2the formation of the selective and accessory substance of the methyl mercaptan of the function of conversion ratio.
Fig. 2 confirms that the formation by increasing titanium dioxide charcoal percent conversion byproducts of carbon monoxide minimizes, and the selective increase of methyl mercaptan.
GHSV=gas hourly space velocity
S=is selective

Claims (26)

1. loaded catalyst, it comprises:
A) containing Mo and the oxygenatedchemicals containing K,
Wherein, Mo and K is optionally the composition of same compound,
B) active oxygenatedchemicals A xo y, wherein A represents Re element, and x and y is the integer of 1-7,
C) carrier,
D) co-catalyst, the general formula that described co-catalyst is selected from transition metal and rare earth metal is M xo yoxygenatedchemicals, wherein x and y is the integer of 1-7 according to the oxidation valency of metal, and,
Replace described rare earth metal or transition metal, or except described rare earth metal or transition metal, formula M xo ym be tin.
2. catalyst as claimed in claim 1, the weight ratio of wherein said compound is:
A xo y/ K 2moO 4/ carrier=0.001/0.01/1-0.5/0.8/1,
A xo y/ MoO 3/ K 2o/ carrier=0.001/0.01/0.005/1-0.5/0.8/0.5/1.
3. catalyst as claimed in claim 2, the weight ratio of wherein said compound is:
A xo y/ K 2moO 4/ carrier=0.001/0.05/1-0.3/0.5/1,
A xo y/ MoO 3/ K 2o/ carrier=0.001/0.05/0.03/1-0.3/0.5/0.3/1.
4. catalyst as claimed in claim 1, wherein said transition metal or rare earth metal are selected from Fe, Co, Ni, La, Ce.
5. catalyst as claimed in claim 1, the weight ratio of wherein said compound is:
K 2moO 4/ M xo y/ carrier=(0.01-0.80)/(0.01-0.1)/1,
MoO 3/ K 2o/M xo y/ carrier=(0.10-0.50)/(0.10-0.30)/(0.01-0.1)/1,
Wherein, x and y is the integer of 1-7.
6. catalyst as claimed in claim 5, the weight ratio of wherein said compound is:
K 2moO 4/ M xo y/ carrier=(0.10-0.60)/(0.01-0.06)/1,
MoO 3/ K 2o/M xo y/ carrier=(0.10-0.30)/(0.10-0.25)/(0.01-0.06)/1.
7. catalyst as claimed in claim 1, it comprises oxygenatedchemicals and/or the sulfur-containing compound of Mo, K, elements A and M, optionally, by obtaining described sulfur-containing compound with the oxygenatedchemicals of element described in hydrogen sulfide treatment.
8. the catalyst as described in any one of claim 1-3, wherein said carriers selected from silica, titanium dioxide, zeolite and active carbon.
9. catalyst as claimed in claim 7, wherein said carrier is that aluminium oxide and described catalyst comprise rheium oxide or sulfuration rhenium.
10. catalyst as claimed in claim 8, wherein said carrier is the titanium dioxide containing at least 60% anatase.
The preparation method of 11. catalyst as claimed in claim 1, it comprises the steps:
A) in one or more steps with comprise (a) metal Re compound, as K 2o precursor containing K compound with as (the NH of compound containing Mo 4) 6mo 7o 244H 2o or MoO 3aqueous impregnation described in carrier; Or
B) in one or more steps with the compound and the K that comprise (a) metal Re 2moO 4one or more aqueous impregnation described in carrier;
C) carrier of dry described dipping; With
D) be selected from transition metal or rare earth metal metallic compound aqueous impregnation described in carrier;
E) steps d is replaced) or in steps d) outside, be used as SnO 2precursor tin compound solution impregnation described in carrier.
12. methods as claimed in claim 11, wherein said metal is selected from Fe, Co, Ni, La and Ce.
13. methods as claimed in claim 12, wherein by the CeO of nano-dispersed 2be suspended in a kind of solution for impregnated carrier.
14. methods as described in claim 11 or 12, wherein dipping solution comprises alkylamide, or the organic acid containing at least one carbon atom and at least one acid functional group.
15. methods as claimed in claim 14, wherein said alkylamide is dimethyl formamide or dimethylacetylamide, and described organic acid is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, propiolic acid, vinyl acetic acid, methacrylic acid, crotonic acid, 4-penetenoic acid, sorbic acid, oxalic acid, malonic acid, butanedioic acid, maleic acid, 3-hydroxybutyrate, glutaric acid, adipic acid, citric acid, tartaric acid or ethylenediamino tetraacetic acid.
16. methods as claimed in claim 14, wherein said organic acid is citric acid.
17. methods as claimed in claim 15, wherein said organic acid is citric acid.
18. methods as described in claim 11 or 12, wherein by drying with the catalyst exposure of optional calcination in the high-temperature atmosphere containing hydrogen sulfide.
19. by reacting the oxide of carbon, sulphur and/or hydrogen sulfide and hydrogen in catalysis process, and the optional water existed prepares the method for methyl mercaptan, reaction as described in wherein carrying out under the loaded catalyst as described in any one of claim 1-10 exists.
20. method, wherein CO as claimed in claim 19 1-2/ H 2s/H 2mol ratio be 1/1/0 to 1/8/8, or when utilize in feed elementary sulfur replace H 2during S, reactant CO 1-2/ S/H 2s/H 2mol ratio be 1/1/0/1 to 1/8/8/8.
21. method, wherein CO as claimed in claim 20 1-2/ H 2s/H 2mol ratio be 1/2/1 to 1/4/4, or when utilize in feed elementary sulfur replace H 2during S, reactant CO 1-2/ S/H 2s/H 2mol ratio be 1/2/2/1 to 1/4/4/4.
22. methods as described in claim 20 or 21, wherein by CO 2as the oxide of described carbon.
23. methods as claimed in claim 19, wherein reaction temperature is 200-500 DEG C, and pressure is 5-50 bar.
24. methods as claimed in claim 19, wherein said reaction is carried out in tubular type, fixed bed, catalytic wall micro channel or fluidized-bed reactor.
25. methods as claimed in claim 24, wherein said tubular reactor is multi-tubular reactor.
26. methods as claimed in claim 19, wherein apply 1-10000h -1gas hourly space velocity.
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